WO2014112953A1 - Procédés de préparation à basse température d'une ou plusieurs couches de graphène sur un substrat métallique pour applications anti-corrosion et anti-oxydation - Google Patents

Procédés de préparation à basse température d'une ou plusieurs couches de graphène sur un substrat métallique pour applications anti-corrosion et anti-oxydation Download PDF

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WO2014112953A1
WO2014112953A1 PCT/SG2014/000020 SG2014000020W WO2014112953A1 WO 2014112953 A1 WO2014112953 A1 WO 2014112953A1 SG 2014000020 W SG2014000020 W SG 2014000020W WO 2014112953 A1 WO2014112953 A1 WO 2014112953A1
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metallic substrate
graphene
temperature
layers
styrene
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PCT/SG2014/000020
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English (en)
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Zongyou YIN
Zehui DU
Hua Zhang
Minmin ZHU
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Nanyang Technological University
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Publication of WO2014112953A1 publication Critical patent/WO2014112953A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/186—Preparation by chemical vapour deposition [CVD]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0209—Pretreatment of the material to be coated by heating

Definitions

  • the invention relates to methods of preparing one or more graphene layers on a metallic substrate for anti-corrosion and anti-oxidation applications.
  • a coating of paint may be applied on the metallic materials.
  • a thin layer of zinc is formed on metallic materials such as steel and iron using a process known as galvanization.
  • Stainless steel has also been used as a basic building block during fabrication of machines to counter against corrosion. .
  • the invention relates to a method of preparing one or more layers of graphene on a metallic substrate.
  • the method comprises
  • the invention in a second aspect, relates to a metallic substrate comprising one or more graphene layers prepared by a method according to the first aspect.
  • the invention relates to use of a method according to the first aspect or a metallic substrate according to the second aspect in anti-corrosion applications, paint, electronic devices, and magnetic devices.
  • the invention relates to use of a method according to the first aspect or a metallic substrate according to the second aspect in anti-corrosion applications on spacecrafts, submarines, aircrafts, oil tankers, shipping vessels, vehicles, pipelines, sewage pipes, buildings, furniture, decorations, lightings, furnishings, kitchenware, utensils, electronic devices, and in anti-oxidation applications on magnetic devices.
  • FIG. 1 is a schematic diagram depicting chemical vapor deposition (CVD) growth for solid carbon source on substrates according to an embodiment.
  • the CVD process is carried out in a multi-heating-zone CVD system having two heating zones, Heating Zone 1 and Heating Zone 2.
  • the two heating zones may be present in a quartz tube.
  • a solid carbon source is placed at Heating Zone 1, while a metallic substrate such as a metal foil is placed in Heating Zone 2.
  • the metallic substrate is annealed in a hydrogen- containing environment to reduce surface oxides on the metallic substrate.
  • the metallic substrate is a nanostructured material such as nanowires
  • the first temperature is not more than 700 °C, as the nanostructured material is not able to withstand temperatures above 700 °C.
  • a carbon vapor is provided by heating the solid carbon source and contacting the carbon vapor with the metallic substrate to form one or more layers of graphene on the metallic substrate.
  • FIG. 2 A and 2B are graphs showing Raman spectra of (A) graphene grown at 500 °C on steel substrate using polystyrene (PS), polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), and poly(methyl methacrylate) (PMMA) as solid carbon sources, and (B) graphene grown at 500 °C with different layers on steel using PS as carbon source.
  • PS polystyrene
  • PVP polyvinylpyrrolidone
  • PEG polyethylene glycol
  • PMMA poly(methyl methacrylate)
  • FIG. 3 A is a graph showing Raman spectra of graphene grown on zinc/zinc oxide (Zn/ZnO) nanoparticles at 550 °C, 500 °C, and 450 °C.
  • FIG. 3B is a typical scanning electron microscopy (SEM) image for graphene/Zn/ZnO nanoparticles grown at 550 °C. Scale bar in FIG. 3B denotes 100 nm.
  • FIG. 4 A is a graph showing Raman spectra of graphene grown on steel substrate at 600 °C, 550 °C, 500 °C, 480 °C, and 450 °C.
  • FIG. 4B depicts typical Raman mapping of D, G, and 2D peak of graphene grown , on steel at 450 °C.
  • the scale bar in images represents 3 ⁇ .
  • FIG. 5A is a graph showing Raman spectra of graphene grown on nickel nanowires at 600 °C, 550 °C, 500 °C, 450 °C, and 400 °C.
  • FIG. 5B depicts typical mapping image of D, G, and 2D peak position graphene grown on nickel at 400 °C. The scale bar in images represents 3 ⁇ .
  • FIG. 5C shows a typical SEM image of nickel nanowires. Scale bar in the image represents 100 nm.
  • FIG. 6 is a graph showing typical Raman spectra of graphene film grown on steel or nickel at 550 °C with the carbon source temperature at 320 °C, 360 °C, and 400 °C.
  • FIG. 7 is a graph showing typical Raman spectra of graphene film grown on steel or nickel at 550 °C at the gas flow of 400 seem, 300 seem, and 200 seem.
  • FIG. 8 shows optical images of (A) steel; and (B) graphene/steel substrate before and after anti-corrosion testing for 24 hours.
  • Scale bar in the figures denote 100 ⁇ .
  • FIG. 9 shows current-voltage curves and corrosion data of graphene grown on steel in a 5 % sea-salt solution.
  • A Tafel plots of steel and graphene/steel (G/steel).
  • B Corrosion rates of steel and G/steel extracted from Tafel plots.
  • C The dependence of the current-voltage curves vs time.
  • Y-axis current (A/cm 2 );
  • D The corrosion potentials and rate as a function of the time in the G/steel samples.
  • FIG. 10 are optical images of (A) Zn/ZnO/ITO; and (B) graphene/Zn ZnO/ITO before and after anticorrosion testing for 24 hours.
  • FIG. 11 is (A) a graph showing current- voltage curves test in 5 % sea-salt solution; and (B) a graph showing light transmittance curve for graphene/Zn/ZnO/ITO.
  • y-axis current (A/cm 2 );
  • x-axis E (V).
  • y-axis transmittance (%);
  • x-axis wavelength (nm).
  • FIG. 12 shows magnetization stability from pure Ni nanowires vs graphene/Ni nanowires for (A) as-prepared samples; and (B) after heating in air at 200 °C for 4 hours.
  • Y- axis magnetization (emu/g);
  • x-axis magnetic field intensity (Oe).
  • Methods disclosed herein allow preparation of one or more graphene layers at low temperature on bulk or nanostructured metallic materials.
  • the method allows preparation of one or more graphene layers on steel and zinc, which are less active, hence posing greater difficulties for depositing graphene thereon.
  • Number of graphene layers on the substrate may be controlled easily by varying process gas flow into the system.
  • use of low cost and widely available starting materials, such as polystyrene and poly(methyl methacrylate) as solid carbon source, and favorable processing conditions, such as low growth temperatures of 500 °C or lower translates into reliable, cost-effective, energy-saving, and environment-friendly processes attractive for industrial application.
  • the low processing temperatures also allow formation of graphene on nanostructures, as the nanostructures are not able to withstand processing temperatures above 700 °C.
  • Methods disclosed herein may be used as an alternative, or as a supplement, to conventional corrosion protection methods.
  • in situ coating of graphene on stainless steel as an intermediate layer also enhances adherence between the anti-corrosion coating and steels. This translates into longer term of protection and lifetime of the coated materials.
  • the graphene coating is at least substantially transparent, appearance of steel is not unduly affected, and may be more cosmetically pleasing compared to coatings using state of the art anti-corrosion paints.
  • incorporating graphene-coated nanopowders into paint does not affect original color of the paint.
  • the invention relates in a first aspect, to a method of preparing one or more layers of graphene on a metallic substrate.
  • Graphene refers generally to a form of graphitic carbon, in which carbon atoms are covalently bonded to one another to form a two-dimensional sheet of bonded carbon atoms.
  • the carbon atoms may be bonded to one another via sp2 bonds, and may form a 6-membered ring as a repeating unit, and may further include a 5-membered ring and/or a 7-membered ring.
  • two or more sheets of graphene may be stacked together to form multiple stacked layers.
  • the side ends of graphene are saturated with hydrogen atoms.
  • the term "metallic substrate” refers to a substrate which consists entirely of at least one metal, or has at least one layer consisting of at least one metal on a surface of the substrate, such as a metal-coated polymeric substrate.
  • metallic it includes metals in their elemental form, as well as metal alloys.
  • the metallic substrate may comprise or consist of a metal selected from Group 3 to Group 12 of the Periodic Table of Elements, steel, or alloys thereof. In various embodiments, the metallic substrate is selected from the group consisting of zinc, nickel, and steel.
  • the metallic substrates may also be steels containing different types of alloying elements such as carbon steels, nickel steels, nickel-chromium steels, molybdenum steels, chromium steels, chromium-vanadium steels, tungsten steels, nickel-chromium-vanadium steels, or silicon-manganese steels.
  • the metallic substrates can be made of nickel-containing steels such as the steels with the SAE (Society of Automotive Engineers) grade 200 series, 300 series, and 800 series, such as, grade-304 and grade-316 stainless steels.
  • the metallic substrate may be a nanostructured material or a non-nanostructured material.
  • nanostructured material refers to a material with at least one dimension in the nanometer range. In various embodiments, at least one dimension of the nanostructured material is less than 1000 nm, such as a length in the range from about 1 nm to about 1000 nm, about 1 nm to about 500 nm, about 1 nm to about 300 nm, about 1 nm to about 200 nm, about 1 nm to about 100 nm, about 1 nm to about 50 nm
  • the metallic substrate is a nanostructured material.
  • nanostructured material include nanoparticles, nanopowder, nanorods, nanopillars, nanowires, nanotubes, nanodiscs, nanoflowers, nanoflakes, nanofilms and foams with wall thickness or pore sizes at nano scales.
  • the metallic substrate is a nanostructured material selected from the group consisting of a nanopowder, a nanoparticle, a nanowire, and combinations thereof.
  • the metallic substrate is a nanopowder or a nanowire.
  • non-nanostructured material which is used interchangeably with the term “bulk material”, refers to a material that does not have at least one dimension in the nanometer range. Accordingly, the terms “nanostructured material” and “non-nanostructured material” refer to two types of materials that are mutually exclusive to each other.
  • the metallic substrate is a non-nanostructured or bulk material, such as a foil, a plate, a plank, a slab, a rod, a ribbon, or combinations thereof.
  • the metallic substrate may be commercially available, finished articles such as fasteners, bolts, screws, washers, nuts, latches, threaded rods, threaded inserts, or combinations thereof.
  • the graphene is deposited or coated on a metallic substrate, such that the graphene is in contact with the at least one metal comprised in the metallic substrate.
  • the graphene is deposited or coated on a surface of the substrate having a layer of at least one metal coated thereon, such that the graphene is in contact with the layer consisting of at least one metal.
  • the method includes annealing a metallic substrate at a first temperature in a range of about 600 °C to about 800 °C in a hydrogen-containing environment to reduce surface oxides on the metallic substrate.
  • annealing refers to heating or subjecting a material to elevated temperatures for a period of time.
  • the annealing is carried out in a hydrogen- containing environment, meaning that the metal substrate is heated in the presence of hydrogen gas, which may be present alone or in combination with other inert gases such as noble gases, for example helium, neon, argon and krypton; nitrogen, or mixtures thereof.
  • hydrogen gas which may be present alone or in combination with other inert gases such as noble gases, for example helium, neon, argon and krypton; nitrogen, or mixtures thereof.
  • the hydrogen-containing environment is essentially free or completely free of oxygen.
  • metal oxides that may be present on a surface of the metallic substrate are reduced to their corresponding metal(s).
  • Annealing a metallic substrate at a first temperature in a hydrogen-containing environment may be carried out for any suitable temperature that allows reduction of the surface oxides.
  • the first temperature is not more than 700 °C when the metallic substrate is a nanostructured material.
  • the first temperature is in a range of about 600 °C to about 800 °C.
  • the first temperature may be in a range of about 650 °C to about 800 °C, about 700 °C to about 800 °C, about 752 °C to about 800 °C, about 600 °C to about 750 °C, about 600 °C to about 700 °C, about 600 °C to about 650 °C, about 650 °C to about 750 °C, or about 650 °C to about 700 °C.
  • the first temperature is in a range of about 600 °C to about 700 °C, such as about 600 °C to about 650 °C, about 650 °C to about 700 °C, about 600 °C, about 650 °C, or about 700 °C.
  • Time period for annealing may depend on the temperature and metallic substrate used.
  • annealing a metallic substrate at a first temperature in a hydrogen-containing environment is carried out for a time period in a range of about 10 minutes to about 20 minutes.
  • annealing the metallic substrate may be carried out in a hydrogen- containing environment at about 800 °C for about 20 minutes.
  • annealing the metallic substrate may be carried out in a hydrogen-containing environment at about 700 °C for about 10 minutes.
  • annealing a metallic substrate at a first temperature in a hydrogen-containing environment is carried out in a gas flow comprising or consisting of hydrogen gas.
  • the gas flow may further comprise an inert gas, such as helium, neon, argon and krypton; nitrogen, or mixtures thereof.
  • the inert gas is argon.
  • number of graphene layers on the substrate may be controlled easily by varying process gas flow into the system.
  • One or more layers of graphene such as 2, 3, 4, 5, or 6 layers of graphene may be prepared on a metallic substrate by varying process gas flow into the system.
  • number of layers of graphene on the metallic substrate is controlled by varying the volumetric ratio of inert gas to hydrogen gas in the gas flow.
  • two layers of graphene are formed on a metallic substrate when argon gas and hydrogen gas flow rates of 200 seem and 15 seem, respectively, are used.
  • the hydrogen gas flow rate is lowered to 8 seem and below, while keeping the argon gas flow rate at 200 seem, multiple layers of graphene may be formed.
  • a monolayer of graphene is formed when argon gas and hydrogen gas flow rates of 200 seem and 40 seem, respectively, are used.
  • the method of the first aspect includes cooling the metallic substrate to a second temperature of around 600 °C or lower for graphene growth. This also means that the maximum temperature that may be used for graphene growth is around 600 °C.
  • the second temperature is in a range of about 400 °C to about 600 °C.
  • the second temperature may be in a range of about 400 °C to about 550 °C, about 400 °C to about 500 °C, about 400 °C to about 450 °C, about 450 °C to about 600 °C, about 450 °C to about 550 °C, or about 500 °C to about 550 °C.
  • the second temperature is in a range of about 400 °C to about 500 °C.
  • the first temperature may be equal to the second temperature. This means that both the first temperature and the second temperature are about 600 °C or lower.
  • the method of the first aspect includes providing a carbon vapor and contacting the carbon vapor with the metallic substrate to form one or more layers of graphene on the metallic substrate.
  • the one or more layers of graphene is formed on the metallic substrate at the second temperature.
  • Providing a carbon vapor is carried out by heating a solid carbon source at a suitable temperature in a range of about 200 °C to about 400 °C such that the solid carbon source decomposes to form the carbon vapor.
  • the solid carbon source may be heated in a hydrogen-containing environment, such as in a gas flow comprising or consisting of hydrogen gas, which may further include an inert gas. Examples of inert gases have already been described above. In various embodiments, the inert gas is argon.
  • the solid carbon source may be a carbon-containing material, such as carbon black, amorphous carbon, activated carbon, graphene, and graphene oxide, and polymers.
  • the solid cafbon source comprises or consists essentially of an aromatic polymer.
  • aromatic polymer refers to a polymer containing at least one aromatic ring in the monomer unit constituting the polymer.
  • the aromatic polymer may be polystyrene (PS), acrylonitrile butadiene styrene(ABS), styrene acrylonitrile (SAN), styrene-isoprene-styrene (SIS), poly(styrene- butadiene- styrene) (SBS), poly(styrene-ethylene butylene-styrene) (SEBS), and various other styrene copolymers, polybutadiene, polyisoprene, polyethylene-butylene, phenolic resins, phenol formaldehyde resins and various other phenolic copolymers, epoxy resins, nylon, polyurethane and their copolymers and the like.
  • the solid carbon source is polyethyl glycerol, poly(methyl methacrylate), polyvinylpyrrolidone, combinations thereof, or copolymers thereof.
  • the temperature used for heating the solid carbon source may be any suitable temperature in a range of about 200 °C to about 400 °C that allows decomposition of the solid carbon source to form the carbon vapor. Depending on the solid carbon source, different temperatures may be used. In various embodiments, the solid carbon source is heated at about 400 °C to form the carbon vapor.
  • the temperature used for heating the solid carbon source may be in a range of about 200 °C to about 350 °C, about 200 °C to about 300 °C, about 200 °C to about 250 °C, about 250 °C to about 400 °C, about 300 °C to about 400 ' °C, about 350 °C to about 400 °C, about 200 °C, about 300 °C, or about 400 °C.
  • the carbon vapor is contacted with the metallic substrate to form one or more layers of graphene on the metallic substrate.
  • the carbon vapor may diffuse near or on a surface of the metallic substrate and deposit thereon. In so doing, islands of carbon are formed on the surface of the metallic substrate. As more carbon vapor contacts the metallic substrate, the islands grow and eventually merge to yield a continuous graphene film.
  • contacting the carbon vapor with the metallic substrate is carried out in a flow of carbon vapor.
  • the carbon vapor may be formed and allowed to flow over the metallic substrate, such that the carbon vapor diffuses on a surface of the metallic substrate, and precipitates or nucleates on the metallic substrate to form islands of carbon upon contact with the carbon vapor.
  • the carbon vapor has a flow rate in a range of about 200 seem to about 400 seem. In specific embodiments, the carbon vapor has a flow rate of about 200 seem.
  • the one or more layers of graphene is grown or formed on the metallic substrate at the second temperature. Suitable ranges of the second temperature that may be used have already been described above.
  • Contacting the carbon vapor with the metallic substrate may be carried out for any suitable time period that allows forming a layer of graphene on the metallic substrate. This may depend, for example, on the temperature used for graphene growth. In various embodiments, contacting the carbon vapor with the metallic substrate is carried out for a time period of about 40 minutes.
  • the invention in a second aspect, relates to a metallic substrate comprising a graphene layer prepared by a method according to the first aspect.
  • metallic substrates that may be used have already been mentioned above.
  • One or more layers of graphene, such as 2, 3, 4, 5, or 6 layers of graphene may be deposited on a surface of the metallic substrate.
  • methods disclosed herein allow preparation of one or more graphene layers on metallic materials, in particular on steel and zinc, which have very low catalytic activity for graphene growth, hence posing greater difficulties for depositing graphene.
  • the methods disclosed herein may advantageously be used to prepare one or more graphene layers on nanostructured materials, given that low processing temperatures of not more than 700 °C, which is below the tolerable or workable temperature ranges of the nanostructured materials, may be used.
  • the invention relates in a further aspect to use of a method according to the first aspect or a metallic substrate according to the second aspect in anti-corrosion applications, paint, and in anti-oxidation for electronic devices and magnetic devices.
  • the invention relates to use of a method according to the first aspect or a metallic substrate according to the second aspect in anti-corrosion applications on spacecrafts, submarines, aircrafts, oil tankers, shipping vessels, vehicles, pipelines, sewage pipes, buildings, furniture, decorations, lightings, furnishings, kitchenware, utensils, and in anti-oxidation for electronic devices and magnetic devices.
  • the term "and/or” includes any and all combinations of one or more of the associated listed items. It will be understood that, although the terms first, second, third, etc., may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another region, layer or section. Thus, a first element, component, region, layer or section discussed below could be termed a second element, component, region, layer or section without departing from the teachings of the present invention.
  • Exemplary embodiments include use of a multi-heating zone furnace and solid carbon sources e.g. polystyrene (PS) to grow graphene.
  • solid carbon sources e.g. polystyrene (PS)
  • PS polystyrene
  • PEG polyethyl glycerol
  • PMMA poly(methyl methacrylate)
  • PVP polyvinylpyrrolidone
  • Example 1 Multi-heating zone CVD system for graphene growth
  • FIG. 1 A schematic diagram of the multi-heating-zone CVD system used in the experiments is shown in FIG. 1.
  • the multi-heating-zone CVD system includes two heating zones, Heating Zone 1 and Heating Zone 2.
  • Heating Zone 1 Generally, a small ceramic container containing a solid carbon source is placed at Heating Zone 1, while metal substrate/nanopowder is placed in Heating Zone 2.
  • the temperature in Heating Zone 2 is set to a temperature in the range of about 600 °C to about 800 °C and the metal substrates/nanopowders are annealed in a 150 seem hydrogen gas flow for about 20 minutes, to convert surface oxides into their corresponding metals. Following this, the metal substrates/nanopowders are cooled down to the desired graphene growth temperature.
  • the nanopowders were put onto a pre- cleaned glass substrate, having thin layer coverage on the glass substrate. Metal oxides on the surface of the nanopowders are reduced to the corresponding metals by annealing under hydrogen gas. At the proper growth temperature, graphene may be grown onto surface of nanopowders when carbon source vapor arrives after flowing from Heating Zone 1.
  • Solid carbon source e.g. PS
  • 400 °C Solid carbon source
  • the active carbon vapor flows over the metallic substrates/templates at Heating Zone 2, it deposits and/or diffuses onto metal surface where it is transformed to graphene.
  • Typical growth time is about 40 minutes. After growth, the furnace cover is opened and cooled down to room temperature.
  • Example 2 Low-temperature synthesis of graphene on bulk or nano-template metals
  • Steel substrates, zinc or nickel nanostructural templates are rinsed by acetone, alcohol, deionized-water, followed by annealing at a temperature in the range of 600 °C to 800 °C in a 150 seem hydrogen gas (H 2 ) flow for 20 minutes.
  • the substrates/templates are then cooled to various growth temperatures of 450 °C, 480 °C, 500 °C, 550 °C, or 600 °C.
  • solid carbon source e.g. PS is heated to form carbon vapor, and graphene growth is initiated when the carbon vapor contacts the metallic templates. Growth time is about 40 minutes.
  • FIG. 2A shows Raman spectra of prepared graphene films on steel.
  • flow rate of argon gas and hydrogen gas for example, different number of layers of graphene on steel may be prepared as shown in FIG. 2B.
  • Method of preparing graphene as disclosed herein may also be grown on Zn metallic nanopowders, as indicated by FIG. 3A and 3B.
  • decomposition temperature of solid carbon source affects the quality of graphene.
  • three different temperatures of 320 °C, 360 °C, and 400 °C as applied on PS were used.
  • FIG. 6 shows typical Raman spectra of the graphene grown on steel or nickel at 550 °C. As temperature increases, the D band gradually reduces, and almost disappears when the carbon source temperature is 400 °C. This indicates that carbon source temperatures at 400 °C or higher are optimal to grow low-defect graphene.
  • Example 4 Gas flow rate
  • FIG. 7 shows typical Raman spectra of graphene grown on steel or nickel at 550 °C with different gas flow, ranging from 200 seem to 400 seem. As gas flow increases, the D band gradually increases, which indicates the quality of graphene films is degraded. From the results obtained, it may be seen that gas flow rate at about 200 seem is best for graphene growth.
  • Example 5 Potential commercial applications [0087] This work has demonstrated a general approach to fabricate large-area and low- defect graphene at low temperatures. The graphenes obtained can offer many potential applications in the following areas.
  • Example 5.1 As replacement for galvanized steels
  • Graphene coated steel may replace galvanized steels in the applications of submarines, aircraft carriers, oil tankers/pipelines and sewage pipes. Compared with the zinc anti-corrosion layers, graphene directly grown on steels offers many advantages, such as better adherence and longer lasting effects.
  • FIG. 8 and 9 show results of tests carried out on anti-corrosion abilities of the graphene-coated steels. From the results shown in FIG. 8B, it may be seen that graphene- coated steels are almost unchanged after subjecting to 24 h accelerated corrosion tests. Steels without coating, on the other hand, are corroded very seriously as shown in FIG. 8A.
  • FIG. 9 further demonstrates enhanced anticorrosion capability of graphene coated steel.
  • the corrosion rate of the G/Steel samples is 2.02 xlO "14 (m/s), a reduction of about 9 times compared to the bare steel without graphene protection (1.75 x 10 " (m/s)).
  • the G-grown steel also demonstrate the excellent lifetime for anticorrosion.
  • the graphene coated steel can therefore replace galvanized steels in many applications, such as submarines, aircraft carriers, oil tankers/pipelines, sewage pipes and spacecrafts.
  • Example 5.2 As fillers in anti-corrosion paints
  • FIG. 10 shows optical images of (A) Zn/ZnO/ITO; and (B) graphene/Zn/ZnO/ITO before and after anticorrosion testing for 24 hours.
  • FIG. 11 is (A) a graph showing current- voltage curves test in 5 % sea-salt solution; and (B) a graph showing light transmittance curve for graphene/Zn/ZnO/ITO.
  • transmittance (%) of the graphene/Zinc coating is as high as above 88%. Therefore, these paints may be used in areas, such as kitchen wares/utensils, ceilings/windows/walls, vehicles' decorations and portable electronic products, where such transparency is required and/or desirable.
  • FIG. 12 shows magnetization stability from pure Ni nanowires vs graphene Ni nanowires for (A) as-prepared samples; and (B) after heating in air at 200 °C for 4 hours.
  • Y- axis magnetization (emu/g);
  • x-axis magnetic field intensity (Oe).
  • graphene coated Ni nanowires may help to enhance stability of electronic and/or magnetic devices from oxidation.
  • Methods as disclosed herein allow preparation of one or more graphene layers on metallic materials such as steel and zinc. They provide important advantages over conventional methods for synthesis of large-area graphene.
  • the graphene growth process is a generalizable process which may be applied to different types of substrate, especially those less active metals.
  • methods developed allow formation of one or more graphene layers on steel and zinc substrates/templates, which are difficult to form graphene on them.
  • As the graphene coating is transparent, appearance of steel is not affected and it is more attractive than those anti-corrosion paints. Consequently, graphene-coated nanopowders, for example, may be incorporated into paint without unduly affecting its transparency.
  • methods disclosed herein involve use of low cost starting materials which are widely and easily available.
  • solid carbon sources such as PS, PVP, PEG and PMMA may be used to form the graphene layers.
  • methods involving very low growth temperatures of 500 °C or lower may be used.

Abstract

La présente invention concerne un procédé de préparation d'une ou plusieurs couches de graphène sur un substrat métallique. Le procédé consiste à recuire un substrat métallique à une première température dans une plage allant d'environ 600 °C à environ 800 °C dans un environnement contenant de l'hydrogène afin de réduire les oxydes sur la surface du substrat métallique ; refroidir le substrat métallique à une seconde température inférieure ou égale à environ 600 °C afin de faire croître le graphène ; fournir une vapeur de carbone par décomposition d'une source de carbone solide à une température dans la plage allant d'environ 200 °C à environ 400 °C et mettre en contact la vapeur de carbone avec le substrat métallique pour former une ou plusieurs couches de graphène sur le substrat métallique à la seconde température. L'invention concerne également des substrats métalliques comprenant une ou plusieurs couches de graphène ainsi préparées, et l'utilisation du procédé et du substrat métallique dans des applications anti-corrosion, des peintures, et dans des applications anti-oxydation pour des dispositifs électroniques et des dispositifs magnétiques.
PCT/SG2014/000020 2013-01-18 2014-01-17 Procédés de préparation à basse température d'une ou plusieurs couches de graphène sur un substrat métallique pour applications anti-corrosion et anti-oxydation WO2014112953A1 (fr)

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CN112813407A (zh) * 2020-12-31 2021-05-18 华东师范大学 一种巨磁阻抗效应石墨烯/纳米晶复合材料及制备方法

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